CN114618435B - 一种竹质颗粒活性炭基催化剂在氰化物防护中的应用 - Google Patents

一种竹质颗粒活性炭基催化剂在氰化物防护中的应用 Download PDF

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CN114618435B
CN114618435B CN202210355959.1A CN202210355959A CN114618435B CN 114618435 B CN114618435 B CN 114618435B CN 202210355959 A CN202210355959 A CN 202210355959A CN 114618435 B CN114618435 B CN 114618435B
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孙昊
马名哲
王亚利
徐茹婷
孙康
蒋剑春
金彦任
赵婷
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Shanxi Xinhua Chemical Defense Equipment Research Institute Co ltd
Institute of Chemical Industry of Forest Products of CAF
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Abstract

本发明公开了一种竹质颗粒活性炭基催化剂在氰化物防护中的应用，属于氰化物防护技术领域。该颗粒活性炭基催化剂以竹加工剩余物制备的炭化料为原料，先与高分子化改性木焦油胶黏剂、塑型剂制得柱状竹质炭原料；然后经热解交联、控氧活化制备得到竹质成型活性炭；再引入复合金属离子得到。与目前的煤质柱状活性炭基催化剂产品相比，本发明使用的林木原料加工副产物更为环保、廉价易得，该催化剂可以更好的应用于氢氰酸和氯化氰防护中，改善目前煤质活性炭防护时间短的问题。

Description

一种竹质颗粒活性炭基催化剂在氰化物防护中的应用
技术领域
本发明属于氰化物防护技术领域，具体涉及一种竹质颗粒活性炭基催化剂在氰化物防护中的应用。
背景技术
活性炭作为一种孔隙结构发达、比表面积大、选择性吸附力强的炭质吸附材料，已经被广泛应用于军工、食品、冶金、化工、环保、医药等行业的精制和净化过程。活性炭及浸渍活性炭是防毒面具滤毒罐及防护器材的核心过滤材料。目前应用较广泛的是ASC-T及ASZM-T型浸渍炭，市场上浸渍炭的载体主要为煤质柱状活性炭，不仅是非再生的，同时存在C、S、N排放高、微孔容积难调控、氰化物防护时间短的问题，亟需开展生物基柱状活性炭替代煤质活性炭载体的研究。
我国具有丰富的竹资源，且竹子具有生长周期短、可再生、零碳排放、加工制品用途广泛等特点，每年产生大量的竹加工剩余物。利用竹加工剩余物制备的竹活性炭具有比表面积大、孔容积高、吸附性能强等优点，但也存在强度差、微孔占比低、不成型、容易造成粉尘等问题，进而限制了竹活性炭产品的应用。目前，通过胶黏剂成型、活化的方法，可以提高制备柱状竹活性炭的强度和比重，但是需要外加煤焦油、沥青等化石类胶黏剂，不仅提高了生产成本和碳排放，同时制备得到的竹质成型活性炭比表面积和孔容积小、微孔率低。
发明内容
针对现有技术中存在的问题，本发明要解决的技术问题在于提供一种竹质颗粒活性炭基催化剂在氰化物防护中的应用，解决目前煤质柱状活性炭催化剂微孔容积小、碳排放高、氰化物防护时间短等问题，解决竹活性炭强度低、不成型的问题，以及解决常规胶黏剂制备柱状活性炭比表面和孔容积小、微孔率低等问题。
为了解决上述问题，本发明所采用的技术方案如下：
一种竹质颗粒活性炭基催化剂在氰化物防护中的应用。
所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，颗粒活性炭基催化剂的制备：成型活性炭与金属溶液混合后，真空浸渍2～10h，130～170℃活化3～10h，产物即为颗粒活性炭基催化剂。
所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，金属溶液为含有Cu、Cr、Ag或Ni一种或多种金属离子的复合水溶液，金属溶液的用量为成型活性炭的饱和吸水量。优选金属离子溶液为含有21wt％Cu、0.4wt％Cr和0.5wt％Ag的复合水溶液。
所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，竹质成型活性炭的制备：将竹加工剩余物制备的炭化料、改性木焦油胶黏剂和羧甲基纤维素钠水溶液真空捏合均匀后，液压成型得到柱状竹质炭原料；然后经过热解交联、控氧活化制备得到高强度、微孔道分布集中的竹质成型活性炭。具体包括以下步骤：
(1)将木焦油副产物与苯酚、甲醛混合，调节溶液pH值为5后，在不同温度下进行梯级反应，减压精馏提纯得到改性木焦油胶黏剂；
(2)将竹加工剩余物炭化料与改性木焦油胶黏剂混合后，加入羧甲基纤维素钠水溶液，真空捏合0.5～3h；所得混合物经过液压成型机制得1～8mm直径的柱状炭，60～100℃干燥处理3～8h；在400～600℃预处理0.5～3h，再在800～900℃温度下控氧水蒸气活化0.5～1.5h，制得竹质成型活性炭。
所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，木焦油副产物为果壳、竹或木材加工剩余物热解产生的副产物，含水量为2％～15％。
所述颗粒活性炭基催化剂在氰化物防护中的应用，羧甲基纤维素钠水溶液的质量浓度为3％。
所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，竹加工剩余物炭化料、改性木焦油胶黏剂与羧甲基纤维素钠的质量比为(3～5):(1～4):(2～5)。
所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，梯级反应为在80、110、130℃温度条件下反应90、20-30和40-50min。
有益效果：与现有的技术相比，本发明的优点包括：
本发明对木焦油进行高分子化交联改性，并将其用作竹炭高压成型的胶黏剂，可有效避免粘结成型过程中胶黏剂进入竹炭的微孔道，减弱对微孔道的堵塞，提高热解过程对炭的交接作用，同时可以提高热解得率，进而不仅可以提升成型活性炭的强度和产率，同时可以提升制备成型活性炭的比表面积、总孔容积和微孔率；相比于化石基胶黏剂，最终制备柱状活性炭的微孔孔径分布更加合理，保证了整个工艺的负碳排放，实现木焦油的规模化和高值化利用；制备的高微孔率活性炭，有利于金属前驱体在微孔道中的高度分散，避免了金属前驱体的过度聚集，进而低温热处理转变为高分散的纳米金属氧化物，制备的竹质柱状活性炭催化剂的氰化物防护时间长。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施例对本发明的具体实施方式做详细的说明。氰化物的防护时间依据标准GJB6239.18-2008、GJB6239.19-2008测试。
竹炭化料的组成为水分4.94％、灰分2.94％、挥发分9.58％、固定碳82.54％，其中碳元素83.97％、氢元素2.11％、氧元素13.33％、氮元素0.59％。
实施例1
竹质成型活性炭的制备：
(1)竹加工剩余物热解产生的焦油(6％含水量)副产物与苯酚、甲醛混合，其中6％含水量焦油副产物与苯酚、甲醛的质量比为12:3:4，采用盐酸调节溶液的pH值至5，在80、110、130℃温度下分别进行梯度反应90、30和40min后，再在80℃减压精馏提纯至水分低于5％，得到改性焦油胶黏剂；
(2)将竹加工剩余物热解得到的炭化料与上述改性焦油胶黏剂混合后，加入3％质量浓度的羧甲基纤维素钠水溶液，炭化料、改性焦油胶黏剂、羧甲基纤维素钠的质量比为10:3:8，进行真空捏合3h；所得混合物经过液压成型机制得4mm直径的柱状炭，在100℃干燥处理6h；在550℃热解交接反应2h，再通过水蒸气活化法850℃无氧活化60min，制得竹质柱状活性炭。
经测定该活性炭强度为95％，比表面积为1013m2/g，总孔容积为0.412cm3/g，微孔率为87％。
竹质颗粒活性炭基催化剂的制备：将上述竹质柱状活性炭与金属离子溶液(含21wt％Cu、0.4wt％Cr、0.5wt％Ag)混合，金属溶液的用量为竹质柱状活性炭的饱和吸水量，真空搅拌浸渍5h，150℃活化6h，得到竹质颗粒活性炭基催化剂。
经测定该催化剂的氯化氰防护时间为31min，氢氰酸防护时间为29min。
对比例1
竹质成型活性炭的制备：将竹加工剩余物热解得到的炭化料(与实施例1用炭化料相同)与沥青混合后，加入3％质量浓度的羧甲基纤维素钠水溶液，炭化料、沥青与羧甲基纤维素钠的质量比为10:3:10，进行真空捏合3h；所得混合物经过液压成型机制得4mm直径的柱状炭，在100℃干燥处理6h；在550℃热解交接反应2h，再通过水蒸气活化法850℃无氧活化60min，制得竹质柱状活性炭。
经测定该竹质柱状活性炭的强度为93％，比表面积为905m2/g，总孔容积为0.361cm3/g，微孔率为76％。
竹质成型活性炭催化剂的制备：将上述竹质成型活性炭与金属离子溶液(含21wt％Cu、0.4wt％Cr、0.5wt％Ag)混合，金属溶液的用量为竹质成型活性炭的饱和吸水量，真空搅拌浸渍5h，150℃活化6h，所得竹质成型活性炭催化剂。
经测定上述竹质成型活性炭催化剂的氯化氰防护时间为26min，氢氰酸防护时间为25min。
对比例2
竹质成型活性炭的制备：将竹加工剩余物热解得到的炭化料(与实施例1用炭化料相同)与未改性焦油(6％含水量)混合后，加入3％质量浓度的羧甲基纤维素钠水溶液，炭化料、6％含水量未改性焦油、羧甲基纤维素钠的质量比为10:3:9，进行真空捏合3h；所得混合物经过液压成型机制得4mm直径的柱状炭，在100℃干燥处理6h；在550℃热解交接反应2h，再通过水蒸气活化法850℃无氧活化60min，制得竹质柱状活性炭。
经测定该竹质柱状活性炭的强度为91％，比表面积为934m2/g，总孔容积为0.348cm3/g，微孔率为78％。
竹质成型活性炭催化剂的制备：将竹质成型活性炭与金属离子溶液(含21wt％Cu、0.4wt％Cr、0.5wt％Ag)混合，金属溶液的用量为竹质成型活性炭的饱和吸水量，真空搅拌浸渍5h，150℃活化6h，所得竹质成型活性炭催化剂。
经测定上述竹质成型活性炭催化剂的氯化氰防护时间为27min，氢氰酸防护时间为25min。
实施例2
竹质成型活性炭的制备：
(1)杏壳热解产生的焦油(5％含水量)副产物与苯酚、甲醛混合，其中5％含水量焦油副产物与苯酚、甲醛的质量比为12:2:3，采用盐酸调节溶液的pH值至4，在80、110、130℃温度下分别进行梯度反应90、20和50min后，再在80℃减压精馏提纯至水分低于5％，得到改性焦油胶黏剂；
(2)将竹加工剩余物热解得到的炭化料与上述改性焦油胶黏剂混合后，加入3％质量浓度的羧甲基纤维素钠水溶液，炭化料、改性焦油胶黏剂与羧甲基纤维素钠的质量比为10:3:8，进行真空捏合3h；所得混合物经过液压成型机制得4mm直径的柱状炭，在100℃干燥处理6h；在550℃热解交接反应2h，再通过水蒸气活化法850℃无氧活化80min，制得竹质柱状活性炭。
经测定上述竹质柱状活性炭的强度为94％，比表面积为1201m2/g，总孔容积为0.506cm3/g，微孔率为85％。
颗粒活性炭基催化剂的制备：将上述竹质成型活性炭与金属离子溶液(含21wt％Cu、0.4wt％Cr、0.5wt％Ag)混合，金属溶液的用量为竹质成型活性炭的饱和吸水量，真空搅拌浸渍5h，140℃活化6h，所得杏壳成型活性炭催化剂。
经测定上述杏壳成型活性炭催化剂的氯化氰防护时间为35min，氢氰酸防护时间为32min。

Claims (4)

1.一种竹质颗粒活性炭基催化剂在氰化物防护中的应用，其特征在于，颗粒活性炭基催化剂的制备：成型活性炭与金属溶液混合后，真空浸渍2~10h，130~170℃活化3~10h，产物即为颗粒活性炭基催化剂；
金属溶液为含有Cu、Cr、Ag或Ni一种或多种金属离子的复合水溶液，金属溶液的用量为成型活性炭的饱和吸水量；
竹质成型活性炭的制备：将竹加工剩余物制备的炭化料、改性木焦油胶黏剂和羧甲基纤维素钠水溶液真空捏合均匀后，液压成型得到柱状竹质炭原料；然后经过热解交联、控氧活化制备得到高强度、微孔道分布集中的竹质成型活性炭；
竹质成型活性炭的制备具体包括以下步骤：
（1）将木焦油副产物与苯酚、甲醛混合，调节溶液pH值为5后，在不同温度下进行梯级反应，减压精馏提纯得到改性木焦油胶黏剂；梯级反应为在80、110、130℃温度条件下反应90、20-30和40-50min；
（2）将竹加工剩余物炭化料与改性木焦油胶黏剂混合后，加入羧甲基纤维素钠水溶液，真空捏合0.5~3h；所得混合物经过液压成型机制得1~8mm直径的柱状炭，60~100℃干燥处理3~8h；在400~600℃预处理0.5~3h，再在800~900℃温度下控氧水蒸气活化0.5~1.5h，制得竹质成型活性炭。
2.根据权利要求1所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，其特征在于，木焦油副产物为果壳、竹或木材加工剩余物热解产生的副产物，含水量为2%~15%。
3.根据权利要求1所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，其特征在于，羧甲基纤维素钠水溶液的质量浓度为3%。
4.根据权利要求1所述竹质颗粒活性炭基催化剂在氰化物防护中的应用，其特征在于，竹加工剩余物炭化料、改性木焦油胶黏剂与羧甲基纤维素钠的质量比为(3~5):(1~4):(2~5)。
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